Long-chain secondary alkyl n-substituted polymeric styrene/maleamic acids and dispersions containing them



Patented Oct. l2, 1948 UNITED STAT-es PATENT OFFICE STITUTED POLYMERIC vS'lYllllINE/MALl!- AMI() ACIDS AND DISPERSIQNS CONTAIN- 'ING THEM,

Witty Lysle Alderson. Jr., Wilmington, Del.. aa-

slgnor to E. I. du Pont de Nemours Company. Wilmington, Pel.. a corporation of Delaware,

ne Drawing. Application Apru so, 194s, serial No. 666.116

9 Claims. l

I'his invention. relatesto dispersing agents, to

which are effective in rendering textiles water-y repellent. to textile vmaterials rendered waterrepellent thereby. andv to methods for the preparation' oi the new N-sllbstitutedpolylnerlc amic acids.

An object `oi this invention is te provide new lil-substituted polymeric. amic ajcids and methods for their preparation. A. .further object of this invention is Vto provide selected-N-substitutcd .polymeric amic acids that are eective in renderins textile materials water-repellent. .Another object `isto provide coating compositions containing novel dispersinig agents and methods (pr rendering textiles water-repellent. An additional object is toprovlde water-repellent coatlns and water-repellent textile materials. Other objects will appear hereinafter.

These objects are accomplished .byN-substituted polymeric amic acids obtainable by reacting one mole equivalent ol a styrene/maleic anhydride intel-polymer 'with from 0.2 toj0.8 mole equivalent of long chain secondary alkyl amines and from 0.8 to 0.4 mole equivalent of Vone or more substances selected .from the class consistlng of ammonia and lower primary amines. The ammonium salts of these N-substituted polymeric amic acids are 'obtainable by reacting them with gaseous or aqueousV ammonia, for example 28% ammonium hydroxide. The equivalent molecular weight of the styrene/,maleic anhydride interpoiymer is considered as being that oi .the structural unit, that is In a preferred method of preparing the N- substituted polymeric 'amic acids, the styrene/maleic anhydride polymer is reacted with from 0.2 to 0.6 mole equivalent ofY a long chain secondary alkyl amine at a temperature in the range of from to 150 C.. in the presence of a. suitable solvent tor the styrene/maleic anhydride polymer; e. g., methyl ethyl ketone. acetone, or dlox-ane. the .reaction mix-ture is cooled to room temperature and then there is added from 0.8 to 0.4 mole equivalent oi oneor more substances selected from the class consisting of ammonia. and the lower primary amines. The reaction may be' carried out by reacting the styrene-maleic anhydxide interpolymer with a mixture of a.- lons chain secondary alkyl. amine andbne or more of the` substances ammonia and lower primary amines in the specified mole proportions. The resulting product is isolated by lt'ration or by other means known to the art.

By "long chain secondary alkyl amine" as used herein islmeant secondary alkyl. amines in which the total number of carbon atoms in the combined alkyl groupsisat least 1B.

By "lower primary amine as used herein is meant primary amines in which .the total .num-

her of carbon atoms in the hydrocarbon group is less than seven. Lower primary ax'nines of this type may be alkyl amines, aryl amines. aralkyl amines. or cycloaliphatic amines. h The new products of this invention include N.- substituted polymeric styrene/maleamic acids or their ammonium salts in which 20 to '60% of the amide nitrogen atoms have two aliphatic hydrocarbon substituents containing a. total of at least 18 carbon atoms in their combined chains and the residual amide groups are selected from the class consisting of unsubstit'uted amide groups and -amide groups having a single monovalent hydrocarbon substituent containing not 'more than Vsix 'carbon atoms. Particularly preferred new N-substituted polymeric styrene/maleamlc acids are those in which 40 to 50% of the amide nitrogen atoms have two.al'iphatic hydrocarbon substituents containing a total-oi at least 18 carbon atoms in their combined chains and in I which '60%v to 50% of the amide nitrogen atoms are unsubstltuted or contain a short chain alkyl The styrene/maiale anhydride interpolymers used in the practice oi' this invention are those obtained by reacting one mole of maleic anhydride with at least one mole of styrene its-described in U. S. Patents A2,047,398 i'ssued July i4, 1986. and 2,378,629 issued June 19. 1945. In the practice of this invention it is generally preferred to use styrene/maleic anhydride interpolymersranging in viscosity from 0.2 to 650 centlpoises at 25 C., when measured as a 15% solution in methyl ethyl ketone. It is especially desirable -to select styrene/maleic anhydride polymers which range in viscosity from 50 to 200 centipolses at 25 C.. when measured as 15% solutions in methyl ethyl ketone. because the best amic acids from the standpoint of ease of applica-tion to tex-tiles are so obtained. The mixed N-substituted polymeric amic acids .that are preferred because they are dispersible in water and at the same time are outstanding in imparting water-repellency to tex- :sample I a Twenty parts of a styrene/maleic anhydride polymer having a viscosity of about 100 centipolses (measured as a solution at 25 C. in

Vmethyl ethyl ketone) and 23.4 parts of diocta- The above example is duplicated using ditetradecylam-ine with similar results.

Example II Twenty parts of the styrene/maiale anhydride polymer of Example I and 23.4Vparts of Vdiocte.- decylamine are reacted as described in Example I. Three and' eight tenths parts of neopentylamine is added and the mixture is allowed to stand for 12 hours at-room temperature. The solution is stirred and 30 parts of 28% ammonium hydroxide is added and the amic acid ammonium salt which separates is collected and dried. The above experiment is duplicated substituting dihexadecylamine for the dioctadecyiamine with analo ous results. f

The abogre example is duplicated substituting methylamine for the neopentylamine with analo- Bous results.

Example Il! Twenty parte of the styrene/maleic anhydride polymer of Example I and 23.4 parts of dloctadecylamine are dissolved in 250 parts of methyl ethyl ketone. To the solution there is added 4.4 parts of aniline andthe mixture is allowed to stand at room temperature for 12 hours. I'lurty parts of 28% ammonium hydroxide is 4then added to the reaction' mixture. The product which separates is collected and dried.

The above example is duplicated substituting -methyioctadecylamine for the dioctadecylam-ine with anaiogous'results.

The above example is duplicated substituting diheptadecylamine for the dioctadecylamine Vwith analogous results;

The above example is duplicated substituting dihexadecylamine for the dioctadecylamine with analogous results.

The above example is duplicated substituting cycldhexylamine for the aniline with analogous results.

The compositions of the above examples are evaluated for their eilectivenes as water repellents for textiles in the following manner.

Five percent aqueous dispersions of the ammonium salts of the amic acids were prepared by stirring their ammonium salts with aqueous ammonium hydroxide at 50-60 C. Nine ounce cotton sateen was then impregnated with these systems in such a manner that the cloth imbibed approximately its own weight of dispersion. The fabrics were then baked for 5 minutes at 170-180" 4 C. in a forced draft oven. 'l'heeifectiveness oi the products aswaterrepelientsisshowninthe V v lnthetablewontrolhreferstothe untreated fabric and the spray rating value indicates that the fabric is 100% water-repellent.

Solids on Faille Emy The spray rating values are obtained as descibed in American Dyestuifs Reporter. 80, 6-14 (l l).

Although in the above test the N-substituted amic acids were applied in the form of aqueous dlsnersions of their ammonium salts it is to be understood that they can also be applied with analogous results from solutions or suspensions in organic solvents.; such as methyl ethyl ketone. dioxane. and the like.

The N-substituted amic acids can be used in the form of solutions or dispersione containing from 2 to- 20% solids. Usually, however. satisfactory results are obtained using dispersions or solutions containing from 5 to 10% of the amic acid Although itfis not necessary. it is sometimes desirable to incorporate inthe N-substitutcd amic acid dispersionel auxiliary dispersing agents, penetrants, pigments, and other modiners to obtain optimum results. Y In order to take full advantage of the waterrepellent capacity of the herein described N-substituted amic acids. it is desirable to heat fabrics that have been impregnated with liquids oontaining in dispersion or solution these products. 'I'he conditions of heating will depend on the chemical nature of the amic acid in question. the

type offabric and the type oi equipment employed. Generally speaking. conditions should be chosen that will cause theV temperature of the treated fabric to rise within the range of 1D0-180 C. If an eillcient forced draft oven is used. this can be accomplished by an exposure of from 1 to 5 minutes at 150-180" C.

As many apparently widely diilerent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specic embodiments thereof except as defined in the appended cl 1. .A process for the preparation of N-substitute'd polymeric amic acids which comprises reacting one moleecuivalent of a styrene/maiale anhydride interpolymex'. having a viscosity from 0.2 to 650 centipoises at 25 C. measured as a 15% solution in methyl ethyl ketone. in a solvent at a temperature of 20 to 150 C., with from 0.2 to 0.6 mole equivalent of a long chain secondary alkyl amine having a total oi' at least 18 carbon atoms in the combined alkyl groups, then adding to the reaction products from 0.8 to 0.4 mole equivalent of at least one of the substances selected from the class consisting of ammonia and lower primary amines containing less than seven carbon atoms.

2. An N.substituted polymeric styrene/maleamic acid in which 20 to 60% of the amide nitrogen atoms have two aliphatic hydrocarbon substituents containing a total of at least 18 carbon atoms in their combined chains, and in which each of the residual amide groups is selected from the class consisting of unsubstituted amide groups and amide groups having a single monovalent hydrocarbon substituent containing less than seven carbon atoms.

3. An N-substituted polymeric styrene/maleamic acid in which 40 to 50% of the amide nitrogen atoms have t'wo aliphatic hydrocarbon substituents containing a total of at least 18 carbon atoms in their combined chains, and in which each of the residual amide groups is selected from the class consisting of unsubstituted amide groups and amide groups having a single monovalent hydrocarbon substituent containing less than seven carbon atoms.

4. A coating composition containing -a liquid in which is dispersed from 2 to 20% by weight of the ammonium salt of an N-substituted polymerio styrene/maleamic acid in which 20 to 00% ot the amide nitrogen atoms have two aliphatic hydrocarbon substituents containing a total of at least 18 carbon atoms in their combined chains, and in which each oi' the residual amide groups is selected from the class consisting of unsubstituted amide groups and amide groups having a single monovalent hydrocarbon substituent containing less than seven carbon atoms.

5. A coating composition containing s liquid in which is dispersed from 2 to 20% by weight of the ammonium salt of an N-substituted polymeric styrene/maleamic acid in which 40 to 50% oi the amide nitrogen atoms have two aliphatic hydrocarbon substituents containing a total oi' at least 18 carbon atoms in their combined chains. and in which each of the residual amide groups is selected from the class consisting of unsubstituted amide groups and amide groups having a single monovaient hydrocarbon substituent containing less than seven carbon atoms.

6. A method for rendering textiles water-repellent which comprises impregnating a textile material with a liquid containing in dispersion from 2 to 20% by weight oi the ammonium salt ot an N-substituted polymeric styrene/maleamic acid in which 20 to 60% of the amide nitrogen atoms have two aliphatic hydrocarbon substituents containing a total oi at least carbon atoms in their combined chains, and in which each of the residual amide groups is selected from the class consisting o! unsubstituted amide groups and amide groups having a single monovalent hy- 6 droearbon substituent containing less than seven carbon atoms. and then baking the impregnated textile material at a temperature between and C.

7. A method for rendering textiles water-repellent which comprises impregnating a textile -material with a liquid containing in dispersion from 2te 20% by weight of the ammonium salt ot an N-substituted polymeric styrene/maleamic acid in which 40 to 50% of the amide nitrogen atoms have two aliphatic hydrocarbon substituents containing a total of at least 1B carbon atoms in their combined chains. and in which each of the residual amide groups is selected from the class consisting ot unsubstituted amide groups and amide groups having a single monovalent hydrocarbon substituent containing less than seven carbon atoms. and then baking the impregnated textile material at a temperature between 100 and 180 C.

8. An N-substituted polymeric styrene-malsamic acid in which 20 to 60% oi the amide nitrogen atoms have a dioctadecyl group attached thereto. and in which each of the residual amide groups is selected from the class consisting of unsubstituted amide groups and amide groups having a single monovaient lwdrocarbon substituent containing less than seven carbon atoms.

9. A water-repellent fabric impregnated with the baked reaction product of the ammonium salt oi an N-substituted polymeric styrene/maleamic acid in which 20 to 80% of the amide nitrogen atoms have a dioctadecyl group attached thereto and in which each oi' the residual amide groups is selected from the class consisting ot unsubstituted amide groups and amide groups having a single monovalent hydrocarbon substituent containing les; than seven carbon atoms.

WII'I'Y LYBLE ALDERSON. Js.

REFERENCES CITED The following references are oi' record in the ille of this patent:

UNITED STATES PATENTS Number Name Date 2,279,410 Nadeau et al. Apr. 14, 1942 2.313.565 McDowell et al. Mar. 9, i943 2.350.870 Pense Aug. 29, 1044 2,375,960 Stoops May 15, 1945 

